New synthetic procedures to catena-phosphorus cations: preparation and dissociation of the first cyclo-phosphino-halophosphonium salts.
New synthetic procedures to catena-phosphorus cations: preparation and dissociation of the first cyclo-phosphino-halophosphonium salts.
复制标题
链状磷阳离子的新合成程序：第一种环膦基卤磷鎓盐的制备和离解。
DOI：
10.1021/ja907693f
复制
发表时间：
2009
影响因子：
15
通讯作者：
Patrick Seelheim
中科院分区：
文献类型：
--
作者：
J. Weigand;N. Burford;Reagan J Davidson;T. Cameron;Patrick Seelheim
在Me(3)SiOTf或GaCl(3)存在下，PhICl(2)或PCl(5)氯化1，2，3，4-四环己基环四膦(2)提供了一种逐步合成第一环膦氯膦阳离子[Cy(4)P(4)Cl](+)([19](+))和[Cy(4)P(4)Cl(2)](2+)([20](2+))的方法。类似的碘衍生物[Cy(4)P(4)I](+)([17](+))是由2与I(2)在GaI(3)存在下反应得到的四碘盐。阳离子[20](2+)与PME(3)或dmpe反应，使环状骨架解离，形成分别含有[Me(3)PPCyPCyPMe(3)](2+)([27](2+))、[dmpeCyP](2+)([29](2+))和[dmpeCyPCyP](2+)([30](2+))的盐。这些新的阳离子代表了[20](2+)中的[Pcy](2+)和[P(2)Cy(2)](2+)阳离子碎片形成的膦配合物，显示了环膦卤阳离子中膦膦键的配位性质。用核磁共振谱、单晶X-射线结晶学和拉曼光谱对化合物进行了表征。
Chlorination of 1,2,3,4-tetracyclohexyl-cyclo-tetraphosphine (2) by PhICl(2) or PCl(5) in the presence of Me(3)SiOTf or GaCl(3) provides a stepwise approach to salts of the first cyclo-phosphino-chlorophosphonium cations [Cy(4)P(4)Cl](+) ([19](+)) and [Cy(4)P(4)Cl(2)](2+) ([20](2+)). The analogous iodo derivative [Cy(4)P(4)I](+) ([17](+)) is obtained as the tetraiodogallate salt from reaction of 2 with I(2) in the presence of GaI(3). Reactions of the dication [20](2+) with PMe(3) or dmpe effect a dissociation of the cyclic framework resulting in the formation of salts containing [Me(3)PPCyPCyPMe(3)](2+) ([27](2+)), [dmpeCyP](2+) ([29](2+)), and [dmpeCyPCyP](2+) ([30](2+)), respectively. The new cations represent phosphine complexes of the [PCy](2+) and [P(2)Cy(2)](2+) cationic fragments from [20](2+), demonstrating the coordinate nature of the phosphinophosphonium bonds in cyclo-phosphino-halophosphonium cations. The compounds have been characterized by NMR spectroscopy, single crystal X-ray crystallography, and Raman spectroscopy.